CN101633779A - Conductive polyaniline composite electrode material and preparation method thereof - Google Patents
Conductive polyaniline composite electrode material and preparation method thereof Download PDFInfo
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- CN101633779A CN101633779A CN200910094857A CN200910094857A CN101633779A CN 101633779 A CN101633779 A CN 101633779A CN 200910094857 A CN200910094857 A CN 200910094857A CN 200910094857 A CN200910094857 A CN 200910094857A CN 101633779 A CN101633779 A CN 101633779A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005457 ice water Substances 0.000 claims abstract description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002019 doping agent Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 44
- 239000002105 nanoparticle Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 4
- 239000001230 potassium iodate Substances 0.000 claims description 4
- 229940093930 potassium iodate Drugs 0.000 claims description 4
- 235000006666 potassium iodate Nutrition 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 abstract description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 abstract description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229940044927 ceric oxide Drugs 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 101100493705 Caenorhabditis elegans bath-36 gene Proteins 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- MXEJFXMHLHQKRP-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Pb++] Chemical compound [O--].[O--].[Ti+4].[Pb++] MXEJFXMHLHQKRP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NSYYPXSKPGPMBW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].Cl Chemical compound [O-2].[O-2].[Ti+4].Cl NSYYPXSKPGPMBW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OIKYXOSPUNWGTC-UHFFFAOYSA-N oxygen(2-) prop-2-enoic acid zirconium(4+) Chemical compound C(C=C)(=O)O.[O-2].[O-2].[Zr+4] OIKYXOSPUNWGTC-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
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- 239000013047 polymeric layer Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
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Abstract
The invention discloses a conductive polyaniline composite electrode material and a preparation method thereof. The preparation method comprises the steps: adopting nano titanium dioxide, ceria, manganese dioxide, lead dioxide, zirconium dioxide, boron carbide and tungsten carbide as templates; directly polymerizing an aniline monomer on nano granules by an in situ polymerization method; adding a surface active agent by using acid as a doping agent at the ice water bath condition of 10 DEG C to 15 DEG C under the action of an oxidizer; adding the nano granules and the aniline monomer at the mol ratio of 1 to (4 to 10) into a system for reacting; and finally obtaining a powdery conductive polyaniline composite electrode material. The compounded conductive polyaniline composite electrode material has the characteristics of good product performance, high quality, simple operation, convenient operation, high reception ratio, low pollution, higher conductivity, high intensity, good thermal stability, good chemical stability, good electric catalytic activity and the like and can be used for nonferrous metal electrode cathode materials, photoconductive nano devices, super electric containers, field transmitting devices, sensor antistatic materials, electromagnetic shielding materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of conductive polyaniline composite electrode material, belong to chemical advanced composite material fabricating technology field.
Background technology
In conductive polymers, advantage such as polyaniline is good because of its conductivity, and environmental stability is good, and synthesis technique is simple, and raw materials cost is cheap, the conductive polymers of the most possible practical application of being known as.Yet, there is defective in the molecular chain and its conductivity and mechanical property are reduced greatly because its molecular weight is little with traditional method synthetic polyaniline, thereby limited its practical application.
Composite technology, especially composite organic-inorganic material technology have been opened up brand-new field for the research of exploring novel material.Organic and inorganic material by compound can be when keeping each composition material primary characteristic, produce the not available new capability of independent organic or inorganic material, therefore research and exploration novel organic-inorganic matrix material are subjected to scientific worker's extensive attention day by day.
(Mukul B, Suprakas S R.J Appl Polym Sci.2000,77:2948) (Wu Qiuju such as Wu Qiuju such as Biswas, Xue Zhijian, QiZongNeng etc. the polymer journal, 1999,5:551) all reported with the method for intercalation polymeric and synthesized high conductivity polyaniline/montmorillonite composite material.Chinese Academy of Sciences's Beijing chemistry ten thousand plum perfume (or spice) (Wan M X, Li W G.Appl Polym Sci, 1997,73:2129) adopt solution blended process, blend coprecipitation method to synthesize the polyaniline Fe that has magnetic and electroconductibility simultaneously
3O
4Matrix material, but Fe
3O
4The distribution of particulate in the polyaniline matrix is restive, and specific conductivity is lower, and saturation magnetization is little, coercivity H
C≈ 0.Polyaniline Fe is also arranged in recent years
3O
4The research report of nano composite membrane.The Deng Jianguo of the organic institute in Chinese Academy of Sciences Chengdu etc. has synthesized with nanometer Fe
3O
4Particulate is nuclear, and electrically conductive polyaniline is the polyaniline Fe with nucleocapsid structure of shell
3O
4Nano composite material, this material has electroconductibility and magnetic property simultaneously, is expected to obtaining actual application aspect absorption of electromagnetic wave, electromagnetic shielding and the electric demonstration.Other polyaniline function mixture such as polyaniline/CuO (Huang C L, Richard E, Matijevic E; J Colloid and interface Sci, (colloid and interface science journal) 1995,170:275), polyaniline/V
2O
5(Wu C G, Degroot DC, Marcy H O, et al.Chem Mater, (chemical material) 1996,29:8277) grade all has report.The formation mechanism of report sheet mica/polyaniline composite materials such as report W.Jia is that the oxidative polymerization of aniline preferentially carries out at mica surface, thereby generated polyphenyl and coated micaceous nucleocapsid structure composite particles (Jia W, et al.Polymers for Advanced Technologies, (polymkeric substance in the hi-tech) 2002,13 (1): 16-24.). it is nuclear that the new profit of well of Xi'an Communications University etc. has been synthesized with the silicon dioxide microparticle, silica dioxide composite particles (the SD/PANI) (Jing Xinli that electrically conductive polyaniline PANI coats, Wang Yangyong, Zhang Donghua; Material engineering, 2004, (1): 20-24).But with the mineral compound with catalytic activity is nuclear, and electrically conductive polyaniline is that the research of the conductive polyaniline composite electrode material with nucleocapsid structure of shell does not appear in the newspapers as yet, does not also have the application of related invention patent.
Summary of the invention
The purpose of this invention is to provide a kind of conductive polyaniline composite electrode material, this electrode materials contains the dusty material of doping agent, oxygenant, tensio-active agent, inorganic nano-particle and aniline monomer, this electrode materials adopts nano titanium oxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, norbide or wolfram varbide for touching plate, make directly polymerization on nano particle of aniline monomer with situ aggregation method, aniline covers and is wrapped on the nanoparticle, and the molar ratio of inorganic nano-particle and aniline monomer is 1: 4～10.
Another object of the present invention provides the preparation method of conductive polyaniline composite electrode material, has following technological process and step:
(a) at first inorganic nano-particle is done modification and handled, a certain amount of inorganic nano-particle is put in the dense mixing acid, reflux is 8～14 hours under 80～100 ℃ of temperature, and dense mixing acid is nitric acid and vitriolic mixing acid, and both volume ratios are: HNO
3: H
2SO
4=1: 1.5～3; Use the distilled water filtering and washing to neutral then, oven dry at last through grinding 4～8 hours at a high speed, obtains the inorganic nano-particle after the modification;
(b) inorganic nano-particle of getting after a certain amount of above-mentioned modification joins in the acid solution, adds an amount of tensio-active agent again, carries out ultra-sonic dispersion 2～4 hours, then a certain amount of aniline monomer is joined in the acid solution earlier.Subsequently the acid solution of above-mentioned aniline is poured in the nanoparticle suspension of above-mentioned inorganic nano-particle acid solution, carried out ultra-sonic dispersion again 0.5～1.5 hour, after treating that suspension is uniformly dispersed, slowly be added drop-wise to the oxygenant that is dissolved in the acid solution in the reaction solution, and under 10～15 ℃ of ice-water bath conditions, stir, make it reaction, the dropping time was built in 1.5～4 hours; After dropwising, continue to keep frozen water molten 10～15 hours;
(c) at last reaction product is carried out centrifugation, repeatedly to remove impurity and oligopolymer, vacuum-drying 24～36 hours under 30～60 ℃ of temperature subsequently finally obtains pulverous conductive polyaniline composite electrode material with deionized water wash.
In the described combination electrode material, the molar ratio of the add-on of inorganic nano-particle and aniline monomer is 1: 4～10; Described inorganic nano-particle can be any one in titanium dioxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, norbide and the wolfram varbide etc.The mol ratio of aniline monomer and oxygenant is 1: 0.75～1.5, and oxygenant can be any in ammonium persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate and the potassium bichromate etc.As the acid of doping agent with the form of the aqueous solution and join in the system with the dropping mode, acid is 1～2.5 with the scope of the mol ratio of aniline: 1, the concentration range of aqueous acid is 0.5～2.5mol/L, and acid can be any in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, Witco 1298 Soft Acid and the sulphosalicylic acid etc.The scope of the mol ratio of tensio-active agent and aniline is 0.05～0.15: 10, and tensio-active agent can be any in sodium laurylsulfonate, polyoxyethylene glycol and the polyvinyl alcohol.
Characteristics of the present invention are, under 10～15 ℃ of ice-water bath conditions, in acidic aqueous system, use situ aggregation method again, and polymerization prepares conductive polyaniline composite electrode material.With this understanding, aniline can be well on nanoparticle nucleation grow up, and can cover fully and be wrapped on the nanoparticle.Technology of the present invention helps polyaniline at the good growth polymerization of nanoparticle surface, and coats relatively evenly, and the molecular-weight average of the composite material surface polyaniline that finally obtains is bigger, and its chemical property improves greatly.The inventive method is simple, and production cost is low.Conductive polyaniline composite electrode material of the present invention has excellent chemical property, can be used for aspects such as electrode materials, ultracapacitor, feds and transmitter.The non-ferrous metal electrodeposition positive plate that this matrix material is made has good electroconductibility and electro catalytic activity, and has good thermostability and chemical stability, and its long service life is also pollution-free to environmental protection in addition.This conducting polyaniline composite material demonstrates than the higher specific conductivity of general chemistry oxypolymerization synthesized polyaniline, also has the specific conductivity more much higher than mineral compound; Yield of the present invention is than simple in-situ oxidizing-polymerizing synthetic polyaniline height.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Embodiment 1
Technological process and step in the present embodiment are as follows:
(1) at first nano titanium oxide is done modification and handled, get in the dense mixing acid that nano titanium oxide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 1.5, reflux is 8 hours under 80 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 4 hours, obtains the nano titanium oxide after the modification.Because nano titanium oxide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nano titanium oxide of getting after the above-mentioned modification of 0.025mol joins in the 100mL hydrochloric acid soln, the concentration of hydrochloric acid is 0.5mol/L, add 0.0005mol tensio-active agent sodium laurylsulfonate again, carried out ultra-sonic dispersion 2 hours, then the 0.1mol aniline monomer is joined in the 50mL hydrochloric acid soln, the concentration of hydrochloric acid is 0.5mol/L, is poured into subsequently in the suspension of above-mentioned nano titanium oxide hydrochloric acid soln, carries out ultra-sonic dispersion again 0.5 hour; The mol ratio of above-mentioned modified nano-titanium dioxide and aniline monomer add-on is 1: 4, after treating that nano titanium oxide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 10 ℃, the 0.075mol ammonium persulphate that is dissolved in the 50mL 0.5mol/L hydrochloric acid soln slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 1.5 hours; After dropwising, continue to keep ice-water bath 24 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 36 hours under 30 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.15 ohm meter with this electrode slice.
Embodiment 2
Technological process and step in the present embodiment are as follows:
(1) at first nano ceric oxide is done modification and handled, get in the dense mixing acid that nano ceric oxide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 2, reflux is 10 hours under 90 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 6 hours, obtains the nano ceric oxide after the modification.Because nano ceric oxide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nano ceric oxide of getting after the above-mentioned modification of 0.02mol joins in the 100mL sulphuric acid soln, vitriolic concentration is 1mol/L, add the 0.001mol surfactant polyethylene again, carried out ultra-sonic dispersion 3 hours, then the 0.1mol aniline monomer is joined in the 50mL sulphuric acid soln, vitriolic concentration is 1mol/L, is poured into subsequently in the suspension of above-mentioned nano ceric oxide sulphuric acid soln, carries out ultra-sonic dispersion again 1 hour; The mol ratio of above-mentioned modified nano-silica cerium and aniline monomer add-on is 1: 5, after treating that nano ceric oxide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 12 ℃, the 0.1mol hydrogen peroxide that is dissolved in the 50mL 1mol/L sulphuric acid soln slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 2.5 hours; After dropwising, continue to keep ice-water bath 30 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 28 hours under 50 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.23 ohm meter with this electrode slice.
Embodiment 3
Technological process and step in the present embodiment are as follows:
(1) at first nano-manganese dioxide is done modification and handled, get in the dense mixing acid that nano-manganese dioxide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 3, reflux is 14 hours under 100 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 8 hours, obtains the nano-manganese dioxide after the modification.Because nano-manganese dioxide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nano-manganese dioxide of getting after the above-mentioned modification of 0.01mol joins in the 65mL phosphoric acid solution, concentration of phosphoric acid is 2.5mol/L, add the 0.0015mol surface active agent polyvinyl alcohol again, carried out ultra-sonic dispersion 4 hours, then the 0.1mol aniline monomer is joined in the 10mL phosphoric acid solution, concentration of phosphoric acid is 2.5mol/L, is poured into subsequently in the suspension of above-mentioned nano-manganese dioxide phosphoric acid solution, carries out ultra-sonic dispersion again 1.5 hours; The mol ratio of above-mentioned modified nano-silica manganese and aniline monomer add-on is 1: 10, after treating that nano-manganese dioxide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 15 ℃, the 0.15mol Potassium Iodate that is dissolved in the 25mL2.5mol/L phosphoric acid solution slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 4 hours; After dropwising, continue to keep ice-water bath 36 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 24 hours under 60 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.12 ohm meter with this electrode slice.
Embodiment 4
Technological process and step in the present embodiment are as follows:
(1) at first nanometer titanium dioxide lead is done modification and handled, get the plumbous 0.05mol of nanometer titanium dioxide and be put in the dense mixing acid of 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 3, reflux is 14 hours under 100 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 8 hours, obtains the nanometer titanium dioxide lead after the modification.Itself exist because of poly-phenomenon because nanometer titanium dioxide is plumbous, be unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) the nanometer titanium dioxide lead of getting after the above-mentioned modification of 0.01mol joins in the 65mL acetum, the concentration of acetic acid is 2.5mol/L, add the 0.0015mol surface active agent polyvinyl alcohol again, carried out ultra-sonic dispersion 4 hours, then the 0.1mol aniline monomer is joined in the 10mL acetum, the concentration of acetic acid is 2.5mol/L, is poured into subsequently in the suspension of above-mentioned nanometer titanium dioxide lead acetate solution, carries out ultra-sonic dispersion again 1.5 hours; The plumbous mol ratio with the aniline monomer add-on of above-mentioned modified nano-silicaization is 1: 10, after treating that the plumbous suspension of nanometer titanium dioxide is uniformly dispersed, after keeping the frozen water solution temperature to be 15 ℃, the 0.15mol iron trichloride that is dissolved in the 25mL2.5mol/L acetum slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 4 hours; After dropwising, continue to keep ice-water bath 36 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 24 hours under 60 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.09 ohm meter with this electrode slice.
Embodiment 5
Technological process and step in the present embodiment are as follows:
(1) at first nano zirconium dioxide is done modification and handled, get in the dense mixing acid that nano zirconium dioxide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 3, reflux is 14 hours under 100 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 8 hours, obtains the nano zirconium dioxide after the modification.Because nano zirconium dioxide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nano zirconium dioxide of getting after the above-mentioned modification of 0.01mol joins in the 65mL acrylic acid solution, acrylic acid concentration is 2.5mol/L, add the 0.0015mol surface active agent polyvinyl alcohol again, carried out ultra-sonic dispersion 4 hours, then the 0.1mol aniline monomer is joined in the 10mL acrylic acid solution, acrylic acid concentration is 2.5mol/L, is poured into subsequently in the suspension of above-mentioned nano zirconium dioxide acrylic acid solution, carries out ultra-sonic dispersion again 1.5 hours; The mol ratio of above-mentioned modified nano-silica zirconium and aniline monomer add-on is 1: 10, after treating that nano zirconium dioxide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 15 ℃, the 0.15mol Potcrate that is dissolved in the 25mL 2.5mol/L acrylic acid solution slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 4 hours; After dropwising, continue to keep ice-water bath 36 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 24 hours under 60 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.13 ohm meter with this electrode slice.
Embodiment 6
Technological process and step in the present embodiment are as follows:
(1) at first nano boron carbide is done modification and handled, get in the dense mixing acid that nano boron carbide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 3, reflux is 14 hours under 100 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 8 hours, obtains the nano boron carbide after the modification.Because nano boron carbide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nano boron carbide of getting after the above-mentioned modification of 0.01mol joins in the 150mL dodecylbenzenesulfonic acid solution, the concentration of Witco 1298 Soft Acid is 1mol/L, add the 0.0015mol surface active agent polyvinyl alcohol again, carried out ultra-sonic dispersion 4 hours, then the 0.1mol aniline monomer is joined in the 20mL dodecylbenzenesulfonic acid solution, the concentration of Witco 1298 Soft Acid is 1mol/L, be poured into subsequently in the suspension of above-mentioned nano boron carbide dodecylbenzenesulfonic acid solution, carried out ultra-sonic dispersion again 1.5 hours; The mol ratio of above-mentioned modified Nano norbide and aniline monomer add-on is 1: 10, after treating that nano boron carbide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 15 ℃, the 0.15mol potassium bichromate that is dissolved in the 30mL 1mol/L dodecylbenzenesulfonic acid solution slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 4 hours; After dropwising, continue to keep ice-water bath 36 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 24 hours under 60 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.16 ohm meter with this electrode slice.
Embodiment 7
Technological process and step in the present embodiment are as follows:
(1) at first nanometer tungsten carbide is done modification and handled, get in the dense mixing acid that nano boron carbide 0.05mol is put in 1000ml, dense mixing acid is concentrated nitric acid and vitriolic mixing acid, and the ratio of both volumes is: HNO
3: H
2SO
4=1: 3, reflux is 14 hours under 100 ℃ of temperature, filters washing to neutral with distilled water then, and oven dry after clipping the ball mill 8 hours, obtains the nanometer tungsten carbide after the modification.Because nanometer tungsten carbide itself exists because of poly-phenomenon, is unfavorable for industrial applications, after treatment, disperse relatively evenly, dispersity improves.
(2) nanometer tungsten carbide of getting after the above-mentioned modification of 0.01mol joins in the 65mL sulphosalicylic acid solution, the concentration of sulphosalicylic acid is 1mol/L, add the 0.0015mol surface active agent polyvinyl alcohol again, carried out ultra-sonic dispersion 4 hours, the 0.1mol aniline monomer is joined in the 20mL sulphosalicylic acid solution then, the concentration of sulphosalicylic acid is 1mol/L, is poured into subsequently in the suspension of above-mentioned nanometer tungsten carbide sulphosalicylic acid acid solution, carries out ultra-sonic dispersion again 1.5 hours; The mol ratio of above-mentioned modified Nano wolfram varbide and aniline monomer add-on is 1: 10, after treating that nanometer tungsten carbide suspension is uniformly dispersed, after keeping the frozen water solution temperature to be 15 ℃, the 0.1mol ammonium persulphate that is dissolved in the 25mL1mol/L sulphosalicylic acid acid solution slowly is added drop-wise in the reaction solution, and the dropping time was controlled at 4 hours; After dropwising, continue to keep ice-water bath 36 hours.
(3) at last reaction product is carried out centrifugation, with deionized water wash for several times, to remove impurity and oligopolymer, vacuum-drying 24 hours under 60 ℃ of temperature subsequently finally obtains Powdered conductive polyaniline composite electrode material.
The Powdered conductive polyaniline composite electrode material that makes in the foregoing description is put into mould, at normal temperature 300 * 10
6The moulding of Pa pressure lower sheeting makes electrode slice.As test samples, the resistivity that adopts 4 contact processs to record above-mentioned electrode slice is 0.05 ohm meter with this electrode slice.
Embodiment 8
Basic identical with the situation of embodiment 2, just changing nanoparticle is wolfram varbide, and oxygenant is an ammonium persulphate, and other condition is identical with embodiment 2, and the resistivity that finally obtains Powdered conductive polyaniline composite electrode material is 0.025 ohm meter.
Embodiment 9
Basic identical with the situation of embodiment 4, just changing nanoparticle is norbide, and other condition is identical with embodiment 4, and the resistivity that finally obtains Powdered conductive polyaniline composite electrode material is 0.18 ohm meter.
Embodiment 10
Basic identical with the situation of embodiment 6, just changing nanoparticle is titanium dioxide, and other condition is identical with embodiment 6, and the resistivity that finally obtains Powdered conductive polyaniline composite electrode material is 0.09 ohm meter.
In addition, the prepared conductive polyaniline composite electrode material of the foregoing description, under transmission electron microscope, can see in the photo of gained, polyaniline coats nanoparticle very even, form the one layer of polymeric layer at the nanoparticle outer wall, the diameter of the nanoparticle complex body after the coating is in 70～100mm scope.
The advantage of this composite is: conductance height, electro catalytic activity height, intensity height, heat endurance and Chemical stability is good; And technology is simple, and is with low cost.
Claims (7)
1, a kind of conductive polyaniline composite electrode material, it is characterized in that: this electrode materials contains the dusty material of doping agent, oxygenant, tensio-active agent, inorganic nano-particle and aniline monomer, this electrode materials adopts nano titanium oxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, norbide or wolfram varbide for touching plate, make directly polymerization on nano particle of aniline monomer with situ aggregation method, aniline covers and is wrapped on the nanoparticle, and the molar ratio of inorganic nano-particle and aniline monomer is 1: 4～10.
2, conductive polyaniline composite electrode material according to claim 1 is characterized in that described doping agent is any in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, Witco 1298 Soft Acid and the sulphosalicylic acid etc.; Described oxygenant is any in ammonium persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate and the potassium bichromate etc.; Tensio-active agent is any in sodium laurylsulfonate, polyoxyethylene glycol and the polyvinyl alcohol, and the scope of the mol ratio of tensio-active agent and aniline is 0.05～0.25: 10.
3, a kind of preparation method of conductive polyaniline composite electrode material is characterized in that having following technological process and step:
(a) at first inorganic nano-particle is done modification and handled, a certain amount of inorganic nano-particle is put in the dense mixing acid, reflux is 8～14 hours under 80～100 ℃ of temperature, and dense mixing acid is nitric acid and vitriolic mixing acid, and both volume ratios are: HNO
3: H
2SO
4=1: 1.5～3; Use the distilled water filtering and washing to neutral then, oven dry at last through grinding 4～8 hours at a high speed, obtains the inorganic nano-particle after the modification;
(b) inorganic nano-particle of getting after the above-mentioned modification joins in the acid solution, adds tensio-active agent again, carries out ultra-sonic dispersion 2～4 hours, and aniline monomer is joined earlier in another acid solution.Subsequently adding there is the acid solution of aniline monomer to pour in the nanoparticle suspension of above-mentioned inorganic nano-particle acid solution, carried out ultra-sonic dispersion again 0.5～1.5 hour, after treating that suspension is uniformly dispersed, the oxygenant that will be dissolved in again in the acid solution slowly is added drop-wise in the reaction solution, and under 10～15 ℃ of ice-water bath conditions, stir, make it reaction, the dropping time was built in 1.5～4 hours; After dropwising, continue to keep frozen water molten 10～15 hours;
(c) at last reaction product is carried out centrifugation, repeatedly to remove impurity and oligopolymer, vacuum-drying 24～36 hours under 30～60 ℃ of temperature subsequently finally obtains pulverous conductive polyaniline composite electrode material with deionized water wash.
4, conductive polyaniline composite electrode material according to claim 3 is characterized in that in the described combination electrode material that the molar ratio of the add-on of inorganic nano-particle and aniline monomer is 1: 4～10; Described inorganic nano-particle is any one in titanium dioxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, norbide and the wolfram varbide etc.
5, the preparation method of conductive polyaniline composite electrode material according to claim 3, it is characterized in that, the mol ratio of aniline monomer and oxygenant is 1: 0.75～1.5, and oxygenant is any in ammonium persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate and the potassium bichromate etc.
6, the preparation method of conductive polyaniline composite electrode material according to claim 3, it is characterized in that, as the acid of doping agent with the form of the aqueous solution and join in the system with the dropping mode, acid is 1～2.5 with the scope of the mol ratio of aniline: 1, the concentration range of aqueous acid is 0.5～2.5mol/L, and acid is any in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, Witco 1298 Soft Acid and the sulphosalicylic acid etc.
7, the preparation method of conductive polyaniline composite electrode material according to claim 3, it is characterized in that, the scope of the mol ratio of tensio-active agent and aniline is 0.05～0.25: 10, and tensio-active agent is any in sodium laurylsulfonate, polyoxyethylene glycol and the polyvinyl alcohol.
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